Method for forming metal-containing films using metal complexes with chelating O- and/or N-donor ligands

ABSTRACT

A method of forming a film on a substrate using one or more complexes containing one or more chelating O- and/or N-donor ligands. The complexes and methods are particularly suitable for the preparation of semiconductor structures using chemical vapor deposition techniques and systems.

FIELD OF THE INVENTION

This invention relates to methods and complexes for formingmetal-containing films, such as metal or metal alloy films, particularlyduring the manufacture of semiconductor device structures. The complexespreferably include low valent metal, and are particularly suitable foruse in a chemical vapor deposition system.

BACKGROUND OF THE INVENTION

High quality thin oxide films of metals, such asbarium-strontium-titanates and strontium-bismuth-tantalates deposited onsemiconductor wafers have recently gained interest for use in memories(e.g., dynamic random access memory (DRAM) devices, static random accessmemory (SRAM) devices, and ferroelectric memory (FE RAM) devices). Thesematerials have very high dielectric constants and excellent resistanceto fatigue. They also have suitable properties for a variety of otheruses, such as electrooptic materials, pyroelectric materials, andantireflective coatings.

Suitable metal oxides are typically delivered to a substrate in thevapor phase; however, many oxides are difficult to deliver using vapordeposition technology. Many precursors are sensitive to thermaldecomposition. Also, many precursors have vapor pressures that are toolow for effective vapor deposition. For example, molecules containingcertain low-valent metals, such as barium, tend to aggregate, whichcauses poor volatility. Thus, there is a continuing need for methods andmaterials for the deposition of oxide films using vapor depositionprocesses on semiconductor structures, particularly random access memorydevices.

SUMMARY OF THE INVENTION

The present invention provides complexes and methods for formingmetal-containing films, particularly low-valent metal-containing films,on substrates, such as semiconductor substrates or substrate assembliesduring the manufacture of semiconductor structures. The methods involveforming a metal-containing film using a complex containing one or morechelating oxygen- and/or nitrogen-donor ligands. The metal-containingfilm can be used in various metallization layers, particularly inmultilevel interconnects or dielectric layers, in integrated circuitstructures.

The metal-containing film can be a film of a single metal, or it can bea metal alloy containing a mixture of metals, or a metal or mixture ofmetals with one or more metalloids. Furthermore, for certain preferredembodiments, the metal-containing film can be an oxide, nitride,sulfide, phosphide, arsenide, stibnide, selenide, silicilide, orcombinations thereof.

Thus, in the context of the present invention, the term“metal-containing film” includes, for example, relatively pure films ofmain group metals, transition metals, or lanthanides, alloys of thesemetals, as well as complexes of metals or metal alloys with otherelements (e.g., O, N, S, Si, P, As, Sb, and Se), or mixtures thereof.The term “single metal film” refers to relatively pure films of singlemetals. The term “metal alloy film” refers to films of these metals inalloys with or without other metals or metalloids, for example.

One preferred method of the present invention involves forming a film ona substrate, such as a semiconductor substrate or substrate assemblyduring the manufacture of a semiconductor structure, by: providing asubstrate (preferably, a semiconductor substrate or substrate assembly);providing a precursor composition comprising one or more complexes ofthe formula:

wherein: M is any metal (main group, transition metal, lanthanide); eachY group is independently O or N—R³; L is a neutral or or anionic (e.g.,monoanionic or dianionic) supporting ligand; each R group isindependently H, or an organic group; x=0 to 6 (preferably, 0 to 2); n+is the oxidation state of the metal, which is typically 0 to +6; y=n ifL is neutral, y=n−x if L is monoanionic, or y=n−2x if L is dianionic;and forming a metal-containing film from the precursor composition on asurface of the substrate (preferably, a semiconductor substrate orsubstrate assembly). The metal-containing film can be a single metalfilm or an alloy film or an oxide, nitride, chalconide, etc. Using suchmethods, the complexes of Formula I are converted in some manner (e.g.,decomposed thermally) and deposited on a surface to form ametal-containing film. Thus, the film is not simply a film of thecomplex of Formula I.

Complexes of Formula I are neutral complexes and may be liquids orsolids at room temperature. If they are solids, they are preferablysufficiently soluble in an organic solvent or have melting points belowtheir decomposition temperatures such that they can be used in flashvaporization, bubbling, microdroplet formation techniques, etc. However,they may also be sufficiently volatile that they can be vaporized orsublimed from the solid state using known chemical vapor depositiontechniques. Thus, the precursor compositions of the present inventioncan be in solid or liquid form. As used herein, “liquid” refers to asolution or a neat liquid (a liquid at room temperature or a solid atroom temperature that melts at an elevated temperature). As used herein,a “solution” does not require complete solubility of the solid; rather,the solution may have some undissolved material, preferably, however,there is a sufficient amount of the material that can be carried by theorganic solvent into the vapor phase for chemical vapor depositionprocessing.

Yet another method of forming a metal-containing film on a substrate,such as a semiconductor substrate or substrate assembly during themanufacture of a semiconductor structure, involves: providing asubstrate (preferably, a semiconductor substrate or substrate assembly);providing a precursor composition comprising one or more organicsolvents and one or more complexes of Formula I as defined above;vaporizing the precursor composition to form vaporized precursorcomposition; and directing the vaporized precursor composition towardthe substrate to form a metal-containing film on a surface of thesubstrate. Herein, vaporized precursor composition includes vaporizedmolecules of precursor complexes of Formula I either alone or optionallywith vaporized molecules of other compounds in the precursorcomposition, including solvent molecules, if used.

Thus, preferred embodiments of the methods of the present inventioninvolve the use of one or more chemical vapor deposition techniques,although this is not necessarily required. That is, for certainembodiments, sputtering, spin-on coating, etc., can be used.

Methods of the present invention are particularly well suited forforming films on a surface of a semiconductor substrate or substrateassembly, such as a silicon wafer, with or without layers or structuresformed thereon, used in forming integrated circuits. It is to beunderstood that methods of the present invention are not limited todeposition on silicon wafers; rather, other types of wafers (e.g.,gallium arsenide wafer, etc.) can be used as well. Also, methods of thepresent invention can be used in silicon-on-insulator technology.Furthermore, substrates other than semiconductor substrates or substrateassemblies can be used in methods of the present invention. Theseinclude, for example, fibers, wires, etc. If the substrate is asemiconductor substrate or substrate assembly, the films can be formeddirectly on the lowest semiconductor surface of the substrate, or theycan be formed on any of a variety of the layers (i.e., surfaces) as in apatterned wafer, for example. Thus, the term “semiconductor substrate”refers to the base semiconductor layer, e.g., the lowest layer ofsilicon material in a wafer or a silicon layer deposited on anothermaterial such as silicon on sapphire. The term “semiconductor substrateassembly” refers to the semiconductor substrate having one or morelayers or structures formed thereon.

A chemical vapor deposition system is also provided. The system includesa deposition chamber having a substrate positioned therein; a vesselcontaining a precursor composition comprising one or more complexes ofFormula I as described above; and a source of an inert carrier gas fortransferring the precursor composition to the chemical vapor depositionchamber.

The present invention also provides certain complexes of Formula I. Forcomplexes of Formula I wherein both Y groups are oxygen or NR³ groups, Mis a main group metal selected from the group of Groups IA, IIA, IVA,and VA (i.e., Groups 1, 2, 14, and 15) metals or a transition metalselected from the group of Groups IB through VIIB (i.e., Groups 11, 12,and 3-7) metals. For complexes of Formula I wherein one Y group isoxygen and the other is an NR³ group, M is a main group metal,transition metal, or a lanthanide.

The present invention further provides precursor compositions containingone or more organic solvents and one or more, complexes preferably, twoor more, of Formula I wherein M is selected from the groups of Ba, Sr,and Ti, or Bi, Sr, and Ta, or Bi, Sr, and Nb, and the compositionsinclude at least two complexes containing different metals.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional schematic of a thin layer ferroelectricmemory device hying a ferroelectric oxide layer between the electrodes.

FIG. 2 is a cross-sectional schematic of a semiconductor contact or viahaving a metal-containing film deposited in accordance with the methodof the present invention.

FIG. 3 is a perspective view of a chemical vapor deposition coatingsystem suitable for use in the method of the present invention.

FIG. 4 is a perspective view of an alternative chemical vapor depositioncoating system suitable for use in the method of the present invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The present invention provides a method of forming a metal-containingfilm using one or more complexes containing one or more chelating O-and/or N-donor ligands. These complexes are mononuclear (i.e., monomersin that they contain one metal per molecule).

The complexes of Formula I are neutral complexes and may be liquids orsolids at room temperature. Typically, they are solids. If they aresolids, they are sufficiently soluble in an organic solvent to allow forvaporization, they can be vaporized or sublimed from the solid state, orthey have melting temperatures below their decomposition temperatures.Thus, many of the complexes described herein are suitable for use inchemical vapor deposition (CVD) techniques, such as flash vaporizationtechniques, bubbler techniques, and/or microdroplet techniques.Preferred embodiments of the complexes described herein are particularlysuitable for low temperature CVD, e.g., deposition techniques involvingsubstrate temperatures of about 50° C. to about 200° C.

The solvents that are suitable for this application can be one or moreof the following: aliphatic saturated or unsaturated linear, branched,or cyclic (alicyclic) hydrocarbons (C₃-C₂₀, and preferably C₅-C₁₀)aromatic hydrocarbons (C₅-C₂₀, and preferably C₅-C₁₀), halogenatedhydrocarbons, silylated hydrocarbons such as alkylsilanes,alkylsilicates, ethers, polyethers, thioethers, esters, lactones,ammonia, amides, amines (aliphatic or aromatic, primary, secondary, ortertiary), polyamines, nitrites, cyanates, isocyanates, thiocyanates,silicone oils, aldehydes, ketones, diketones, carboxylic acids, water,alcohols, thiols, or compounds containing combinations of any of theabove or mixtures of one or more of the above. It should be noted thatsome precursor complexes are sensitive to reactions with proticsolvents, and examples of these noted above may not be ideal, dependingon the nature of the precursor complex. The complexes are also generallycompatible with each other, so that mixtures of variable quantities ofthe complexes will not interact to significantly change their physicalproperties.

One preferred method of the present invention involves vaporizing aprecursor composition that includes one or more metal complexescontaining one or more chelating O- and/or N-donor ligands. The metalcan be a main group metal, a transition group metal, or a lanthanide.Also, the precursor composition can include complexes containingmetalloids or metals with other ligands.

The precursor composition can be vaporized in the presence of an inertcarrier gas to form a relatively pure metal or metal alloy film. Theinert carrier gas is typically selected from the group consisting ofnitrogen, helium, argon, and mixtures thereof. In the context of thepresent invention, an inert carrier gas is one that is generallyunreactive with the complexes described herein and does not interferewith the formation of a metal-containing film.

Alternatively, however, the precursor composition can be vaporized inthe presence of a reaction gas to form a film. The reaction gas can beselected from a wide variety of gases reactive with the complexesdescribed herein, at least at a surface under the conditions of chemicalvapor deposition. Relatively pure metal or metal alloy films can also beproduced using a reducing gas, such as hydrogen, optionally also using aplasma to enhance the deposition process. Examples of other reactiongases include oxygen, nitrogen oxides, ammonia, hydrazine, water vapor,ozone, hydrogen sulfide, hydrogen selenide, hydrogen telluride, silane,disilane, trichlorosilane, dichlorosilane, and the like. Variouscombinations of carrier gases and/or reaction gases can be used in themethods of the present invention to form metal-containing films. Thus,the metal-containing film can include a nitride, phosphide, arsenide,stibnide, oxide, sulfide, selenide, telluride, silicide, or combinationsthereof. Such metal-containing films can be can also be formed bysubjecting a relatively pure metal film to subsequent processing, suchas annealing or rapid thermal oxidation, to form other metal-containingfilms, such as oxides or silicides, for example.

The complex containing chelating oxygen- and/or nitrogen-donor ligandsis of the following formula:

wherein: M is a metal (main group, transition metal, or lanthanide);each Y group is independently O or N—R³; L is a neutral or anionicsupporting ligand (i.e., one that satisfies the valence state of themetal or completes the coordination sphere); each R group isindependently H or an organic group (preferably, a (C₁-C₈)organicgroup); x=0 to 6 (preferably, 0 to 2); n+ is the oxidation state of themetal, which is typically 0 to +6; y=n if L is neutral, y=n−x if L ismonoanionic, or y=n−2x if L is dianionic; and forming a metal-containingfilm from the precursor composition on a surface of the substrate(preferably, the semiconductor substrate or substrate assembly).

The complexes of Formula I can take the following forms (which arerepresentative only):

For certain methods of the present invention, preferably, M is selectedfrom the group of metals of Groups IIA, IVB, VA, VB, VIIIB, and IB(i.e., Groups 2, 4, 5, 8-11, and 15). More preferably, M is selectedfrom the group of Sr, Ba, Ti, Bi, Ta, Rh, Ir, Pd, Pt, Cu, and Ag. Evenmore preferably, M is Sr, Ba, Ti, or Cu. Most preferably, M is Sr, Ba,or Ti.

For complexes of Formula I wherein both Y groups are oxygen or NR³groups, M is a main group metal selected from the group of Groups IA,IIA, IVA, and VA (i.e., Groups 1, 2, 14, and 15) metals or a transitionmetal selected from the group of Groups IB, IIB, IIIB, IVB, VB, VIB, andVIIB (i.e., Groups 11, 12, and 3-7) metals. More preferably, M isselected from the group of Sr, Ba, Ti, Zr, Ta, Nb, Pb, and Bi. Mostpreferably, M is Sr, Ba, or Ti. For complexes of Formula I wherein one Ygroup is oxygen and the other is an NR³ group, M is a main group metal,transition metal, or a lanthanide. More preferably, M is selected fromthe group of Sr, Ba, Ti, Zr, Ta, Nb, Pb, and Bi. Most preferably, M isSr, Ba, or Ti.

Preferably, L is absent (x=0); however, if it is present, it is selectedfrom the group of dialkyl- and trialkyl-amines, polyamines (e.g.,N,N,N′N′N″-pentamethyldiethylenetriamine, diethylenetriamine),trialkylphosphines, ethers (including linear, branched, and cyclicethers and polyethers), unsubstituted and fluoro-substituted alkyls(including linear, branched, and cyclic alkyls), unsubstituted alkenes(including linear, branched, and cyclic monoenes, dienes, and trienes,such as cyclopentadienyl and cyclooctadienyl), unsubstituted alkynes(including linear, branched, and cyclic alkynes), alkoxy groups (e.g.,methoxy, ethoxy, isopropoxy), carboxylates, diketonates, thiolates,substituted silanes (including alkoxy substituted silanes, alkylsubstituted silanes, alkenyl substituted silanes), as well as oxo,nitrile, and carbonyl ligands. Various combinations of such L groups canbe present in a molecule. More preferably, L is carbonyl,cyclopentadienyl, cyclooctadienyl, ethoxy, isopropoxy,vinyltrimethylsilane, and polyamine.

A preferred class of complexes of Formula I include those in which M isSr or Ba, x=0, y=2, R¹ and R² are each hydrogen or a stericallydemanding alkyl group, such as a t-butyl group and, if present, R³ is asterically demanding alkyl group, such as a t-butyl group. This class ofcomplexes of Formula I is particularly advantageous because the stericdemands of the ligands ensure that the complexes will be mononuclear andsufficiently volatile for CVD.

As used herein, the term “organic group” means a hydrocarbon group (withoptional elements other than carbon and hydrogen, such as oxygen,nitrogen, sulfur, and silicon) that is classified as an aliphatic group,cyclic group, or combination of aliphatic and cyclic groups (e.g.,alkaryl and aralkyl groups). In the context of the present invention,the organic groups are those that do not interfere with the formation ofa metal-containing film. Preferably, they are of a type and size that donot interfere with the formation of a metal-containing film usingchemical vapor deposition techniques. The term “aliphatic group” means asaturated or unsaturated linear or branched hydrocarbon group. This termis used to encompass alkyl, alkenyl, and alkynyl groups, for example.The term “alkyl group” means a unsaturated linear or branchedhydrocarbon group including, for example, methyl, ethyl, isopropyl,t-butyl, heptyl, dodecyl, octadecyl, amyl, 2-ethylhexyl, and the like.The term “alkenyl group” means an unsaturated, linear or branchedhydrocarbon group with one or more carbon-carbon double bonds, such as avinyl group. The term “alkynyl group” means an unsaturated, linear orbranched hydrocarbon group with one or more carbon-carbon triple bonds.The term “cyclic group” means a closed ring hydrocarbon group that isclassified as an alicyclic group, aromatic group, or heterocyclic group.The term “alicyclic group” means a cyclic hydrocarbon group havingproperties resembling those of aliphatic groups. The term “aromaticgroup” or “aryl group” means a mono- or polynuclear aromatic hydrocarbongroup. The term “heterocyclic group” means a closed ring hydrocarbon inwhich one or more of the atoms in the ring is an element other thancarbon (e.g., nitrogen, oxygen, sulfur, etc.).

Substitution is anticipated on the organic groups of the complexes ofthe present invention. As a means of simplifying the discussion andrecitation of certain terminology used throughout this application, theterms “group” and “moiety” are used to differentiate between chemicalspecies that allow for substitution or that may be substituted and thosethat do not allow or may not be so substituted. Thus, when the term“group” is used to describe a chemical substituent, the describedchemical material includes the unsubstituted group and that group withO, N, Si, or S atoms, for example, in the chain (as in an alkoxy group)as well as carbonyl groups or other conventional substitution. Where theterm “moiety” is used to describe a chemical compound or substituent,only an unsubstituted chemical material is intended to be included. Forexample, the phrase “alkyl group” is intended to include not only pureopen chain saturated hydrocarbon alkyl substituents, such as methyl,ethyl, propyl, t-butyl, and the like, but also alkyl substituentsbearing further substituents known in the art, such as hydroxy, alkoxy,alkylsulfonyl, halogen atoms, cyano, nitro, amino, carboxyl, etc. Thus,“alkyl group” includes ether groups, haloalkyls, nitroalkyls,carboxyalkyls, hydroxyalkyls, sulfoalkyls, etc. On the other hand, thephrase “alkyl moiety” is limited to the inclusion of only pure openchain saturated hydrocarbon alkyl substituents, such as methyl, ethyl,propyl, t-butyl, and the like.

Preferably, each R group (R¹, R², and R³) in the complexes of Formula Iis H or a (C₁-C₈) organic group. More preferably, each R group is H or a(C₁-C₅) organic group. Most preferably, each R group is a (C₁-C₄) alkylmoiety.

Various combinations of the complexes described herein can be used in aprecursor composition. Thus, as used herein, a “precursor composition”refers to a liquid or solid that includes one or more complexes of theformulas described herein optionally mixed with one or more complexes orformulas other than those of Formula I. The precursor composition canalso include one or more organic solvents suitable for use in a chemicalvapor deposition system, as well as other additives, such as freeligands, that assist in the vaporization of the desired compounds.Preferred precursor compositions of the present invention include one ormore organic solvents and two or more complexes of Formula I wherein Mis selected from the groups of Ba, Sr, and Ti, or Bi, Sr, and Ta, or Bi,Sr, and Nb. Such precursor compositions include at least two complexescontaining different metals (e.g., Ba and Ti). Preferably, suchprecursor compositions include at least three complexes containingdifferent metals (e.g., Ba, Sr, and Ti).

The complexes described herein can be used in precursor compositions forchemical vapor deposition. Alternatively, certain complexes describedherein can be used in other deposition techniques, such as sputtering,spin-on coating,and the like. Typically, those complexes containing Rgroups with a low number of carbon atoms (e.g., 1-4 carbon atoms per Rgroup) are suitable for use with vapor deposition techniques. Thosecomplexes containing R groups with a higher number of carbon atoms(e.g., 5-12 carbon atoms per R group) are generally suitable for spin-onor dip coating. Preferably, however, chemical vapor depositiontechniques are desired because they are more suitable for deposition onsemiconductor substrates or substrate assemblies, particularly incontact openings which are extremely small and require conformallyfilled layers of metal.

The complexes of the present invention can be prepared by a variety ofmethods known to one of skill in the art. For example,Ba(^(t)Bu—C(O)—N—C(O)—^(t)Bu)₂ can be prepared from the reaction of BaI₂with Li(^(t)Bu—C(O)—N—C(O)—^(t)Bu).

As stated above, the use of the complexes and methods of forming filmsof the present invention are beneficial for a wide variety of thin filmapplications in semiconductor structures, particularly those using highdielectric materials or ferroelectric materials. For example, suchapplications include capacitors such as planar cells, trench cells(e.g., double sidewall trench capacitors), stacked cells (e.g., crown,V-cell, delta cell, multi-fingered, or cylindrical container stackedcapacitors), as well as field effect transistor devices. The complexesand methods of forming films of the present invention can also be usedto prepare metallization layers, such as multilevel interconnects in anintegrated circuit structure.

A specific example of where a film formed from the complexes of thepresent invention would be useful is the ferroelectric memory cell 10 ofFIG. 1. The memory cell 10 includes a ferroelectric material 11, whichis prepared by depositing one or more of the complexes discussed hereinusing chemical vapor techniques, between two electrodes 12 and 13, whichare typically made of platinum, although other metals such as ruthenium,iridium, or gold can also be used. The bottom electrode 13 is typicallyin contact with a silicon-containing layer 14, such as an n-type orp-type silicon substrate, silicon dioxide, glass, etc. A conductivebarrier layer 15 is positioned between the bottom electrode 13 and thesilicon-containing layer 14 to act as a barrier to diffusion of atomssuch as silicon into the electrode and ferroelectric material.

Another example of where a film formed from the complexes of the presentinvention would be useful is the structure shown in FIG. 2. Thestructure may be in the form of an n-channel MOSFET (n-channelmetal-oxide semiconductor field-effect transistor), which may be used ina DRAM memory device. As shown, substrate 16 is a p-type silicon havingtwo n-type silicon islands 20 and 22, representing the transistor sourceand drain. Such a construction is well known. The gate for thetransistor is formed by a metal/polysilicon layer 24 deposited over asilicon dioxide layer 26. A relatively thick layer of an insulatingsilicon dioxide 28 overlies the active areas on substrate 16. A complexof Formula I may be used to vapor deposit one or more portions of layer24.

To connect the MOSFET with electrically conductive paths (i.e., metallines) on the surface of the device, contacts 30 and 32 have been etchedthrough oxide layer 28 down to the surface of substrate 16. A metal ormetal silicide layer 34, such as titanium silicide, is deposited andformed at the base of contact holes 30 and 32. A thin, conformal barrierlayer 36 of a conductive material (e.g., titanium nitride, titaniumaluminum nitride, titanium nitride silicide) is deposited over the wallsof the contact holes 30 and 32. Because of the presence of theconductive barrier layer 36, the electrical contact path is excellentand metal 38 (e.g., Al or Cu), which is deposited over the barrier layer36 is prevented from attacking the substrate surfaces. Complexes ofFormula I may be used to vapor deposit layers 34, 36, or 38, forexample.

Methods of the present invention can be used to deposit ametal-containing film, preferably a metal or metal alloy film, on avariety of substrates, such as a semiconductor wafer (e.g., siliconwafer, gallium arsenide wafer, etc.), glass plate, etc., and on avariety of surfaces of the substrates, whether it be directly on thesubstrate itself or on a layer of material deposited on the substrate asin a semiconductor substrate assembly. The film is deposited upondecomposition (typically, thermal decomposition) of a complex of FormulaI, preferably one that is either a volatile liquid, a sublimable solid,or a solid that is soluble in a suitable solvent that is not detrimentalto the substrate, other layers thereon, etc. Preferably, however,solvents are not used; rather, the transition metal complexes are liquidand used neat. Methods of the present invention preferably utilize vapordeposition techniques, such as flash vaporization, bubbling, etc.

A typical chemical vapor deposition (CVD) system that can be used toperform the process of the present invention is shown in FIG. 3. Thesystem includes an enclosed chemical vapor deposition chamber 60, whichmay be a cold wall-type CVD reactor. As is conventional, the CVD processmay be carried out at pressures of from atmospheric pressure down toabout 10−³ torr, and preferably from about 10 torr to about 0.1 torr. Avacuum may be created in chamber 60 using turbo pump 62 and backing pump64.

One or more substrates 66 (e.g., semiconductor substrates or substrateassemblies) are positioned in chamber 60. A constant nominal temperatureis established for the substrate, preferably at a temperature of about100° C. to about 800° C., and more preferably at a temperature of about50° C. to about 200° C. Substrate 66 may be heated, for example, by anelectrical resistance heater 68 on which substrate 66 is mounted. Otherknown methods of heating the substrate may also be utilized.

In this process, the precursor composition 40, which contains one ormore complexes of Formula I (and/or other metal or metalloid complexes),is stored in liquid form (a neat liquid at room temperature or at anelevated temperature if solid at room temperature) in vessel 42. Asource 44 of a suitable inert gas is pumped into vessel 42 and bubbledthrough the neat liquid (i.e., without solvent) picking up the precursorcomposition and carrying it into chamber 60 through line 45 and gasdistributor 46. Additional inert carrier gas or reaction gas may besupplied from source 48 as needed to provide the desired concentrationof precursor composition and regulate the uniformity of the depositionacross the surface of substrate 66. As shown, a series of valves 50-55are opened and closed as required.

Generally, the precursor composition is pumped into the CVD chamber 60at a flow rate of about 1 sccm (standard cubic centimeters) to about1000 sccm. The semiconductor substrate is exposed to the precursorcomposition at a pressure of about 0.001 torr to about 100 torr for atime of about 0.01 minute to about 100 minutes. In chamber 60, theprecursor composition will form an adsorbed layer on the surface of thesubstrate 66. As the deposition rate is temperature dependent,increasing the temperature of the substrate will increase the rate ofdeposition. Typical deposition rates are about 10 Angstroms/minute toabout 1000 Angstroms/minute. The carrier gas containing the precursorcomposition is terminated by closing valve 53.

An alternative CVD system that can be used to perform the process of thepresent invention is shown in FIG. 4. The system includes an enclosedchemical vapor deposition chamber 160, which may be a cold wall-type CVDreactor, in which a vacuum may be created using turbo pump 162 andbacking pump 164. One or more substrates 166 (e.g., semiconductorsubstrates or substrate assemblies) are positioned in chamber 160.Substrate 166 may be heated as described with reference to FIG. 3 (forexample, by an electrical resistance heater 168).

In this process, one or more solutions 70 of one or more precursorcomplexes of Formula I (and/or other metal or metalloid complexes), arestored in vessels 72. The solutions are transferred to a mixing manifold74 using pumps 76. The resultant precursor composition containing one ormore precursor complexes and one or more organic solvents is thentransferred along line 78 to vaporizer 80, to volatilize the precursorcomposition. A source 84 of a suitable inert gas is pumped intovaporizer 80 for carrying volatilized precursor composition into chamber160 through line 85 and gas distributor 86. Reaction gas may be suppliedfrom source 88 as needed. As shown, a series of valves 90-95 are openedand closed as required. Similar pressures and temperatures to thosedescribed with reference to FIG. 3 can be used.

Alternatives to such methods include an approach wherein the precursorcomposition is heated and vapors are drawn off and controlled by a vapormass flow controller, and a pulsed liquid injection method as describedin “Metalorganic Chemical Vapor Deposition By Pulsed Liquid InjectionUsing An Ultrasonic Nozzle: Titanium Dioxide on Sapphire from Titanium(IV) Isopropoxide,” by Versteeg, et al., Journal of the American CeramicSociety, 78, 2763-2768 (1995). The complexes of Formula I are alsoparticularly well suited for use with vapor deposition systems, asdescribed in copending application U.S. Ser. No. 08/720,710 entitled“Method and Apparatus for Vaporizing Liquid Precursor compositions andSystem for Using Same,” filed on Oct. 2, 1996. Generally, one methoddescribed therein involves the vaporization of a precursor compositionin liquid form (neat or solution). In a first stage, the precursorcomposition is atomized or nebulized generating high surface areamicrodroplets or mist. In a second stage, the constituents of themicrodroplets or mist are vaporized by intimate mixture of the heatedcarrier gas. This two stage vaporization approach provides areproducible delivery for precursor compositions (either in the form ofa neat liquid or solid dissolved in a liquid medium) and providesreasonable growth rates, particularly in device applications with smalldimensions.

Various combinations of carrier gases and/or reaction gases can be usedin certain methods of the present invention. They can be introduced intothe chemical vapor deposition chamber in a variety of manners, such asdirectly into the vaporization chamber or in combination with theprecursor composition.

Although specific vapor deposition processes are described by referenceto FIGS. 3-4, methods of the present invention are not limited to beingused with the specific vapor deposition systems shown. Various CVDprocess chambers or reaction chambers can be used, including hot wall orcold wall reactors, atmospheric or reduced pressure reactors, as well asplasma enhanced reactors. Furthermore, methods of the present inventionare not limited to any specific vapor deposition techniques.

The following examples are offered to further illustrate the variousspecific and preferred embodiments and techniques. It should beunderstood, however, that many variations and modifications may be madewhile remaining within the scope of the present invention.

EXAMPLES Example 1 Synthesis of Ba(^(t)BuC(O)NC(O)^(t)Bu)₂

A Schlenk flask is charged with 10.0 g (26 mmol) of BaI₂, which issuspended in 100 mL of THF. To this is added 104 mL (26 mmol) of 0.5MTHF solution of Li(^(t)BuC(O)NC(O)^(t)Bu), which is prepared by reactingbutyl lithium with ^(t)BuC(O)NHC(O)^(t)Bu. The mixture ofLi(^(t)BuC(O)NC(O)^(t)Bu) and BaI₂ is stirred for 20 hours. The solventis then removed in vacuo. The crude product is extracted from thelithium iodide with hexanes and filtered into another flask. The solventis removed in vacuo yielding a colorless solid, which is furtherpurified by sublimation.

Example 2 Synthesis of Sr(^(t)BuC(O)NC(O)^(t)Bu)₂

This compound is prepared in an analogous manner to the procedureoutlined in Example 1 using SrI₂ as the starting material.

Example 3 Synthesis of Ti (O^(i)Pr)₂(^(t)BuC(O)NC(O)^(t)Bu)₂

A Schlenk flask is charged with 12.0 g (60 mmol) of Ti(O^(i)Pr)₂Cl₂,which is dissolved in 100 mL of THF. To this is added 240 mL (120 mmol)of 0.5M THF solution of Li(^(t)BuC(O)NC(O)^(t)Bu). The mixture ofLi(^(t)BuC(O)NC(O)^(t)Bu) and Ti(O^(i)Pr)₂Cl₂ is stirred for 24 hours.The solvent is then removed in vacuo. The crude product is extractedfrom the lithium chloride with hexanes and filtered into another flask.The solvent is removed in vacuo yielding a colorless solid, which isfurther purified by sublimation.

Example 4 Chemical Vapor Deposition of (Ba, Sr)TiO₃

Solutions of each of the precursors noted in Examples 1-3 are preparedby dissolving the solid compounds in THF to make 0.2M solutions in therespective metal. To the Ba and Sr precursor solutions are also added 1equivalent each of N,N,N′N′,N″-pentamethyldiethylenetriamine tostabilize monomeric precursor species. The solutions are added to threeseparate reservoirs of a CVD system and the liquids are pumped to avaporizer in approximately equal proportions. The vaporizer is heated to190° C., allowing stable vapor transport of the precursor vapor into achamber held at 1 Torr. The substrate (polysilicon on thermally grownsilicon oxide on p-type silicon wafer) is heated to 675° C. Precursorvapor is carried into the chamber using He gas flow of 50 sccm. A flowof 100 sccm oxygen reaction gas is added to the chamber via anotherinlet. Thickness of the deposited film is dependent upon depositiontime. The Ba:Sr:Ti ratio could be manipulated by the individual liquiddelivery rates.

The foregoing detailed description and examples have been given forclarity of understanding only. No unnecessary limitations are to beunderstood therefrom. The invention is not limited to the exact detailsshown and described, for variations obvious to one skilled in the artwill be included within the invention defined by the claims. Thecomplete disclosures of all patents, patent documents, and publicationslisted herein are incorporated by reference, as if each wereindividually incorporated by reference.

What is claimed is:
 1. A method of manufacturing a semiconductorstructure, the method comprising: providing a semiconductor substrate orsubstrate assembly; providing a precursor composition comprising one ormore complexes of the formula:

 wherein: M is a transition metal, main group metal, or lanthanide; eachY group is independently O or N—R³; L is a neutral or anionic supportingligand; each R group is independently H, or an organic group; x=0 to 6;n+ is the oxidation state of the metal; y=n if L is neutral, y=n−x if Lis monoanionic, or y=n−2x if L is dianionic; and forming ametal-containing film from the precursor composition on a surface of thesemiconductor substrate or substrate assembly.
 2. The method of claim 1wherein the step of forming a metal-containing film comprises vaporizingthe precursor composition and directing it toward the semiconductorsubstrate or substrate assembly using a chemical vapor depositiontechnique.
 3. The method of claim 2 wherein the chemical vapordeposition technique comprises flash vaporization, bubbling,microdroplet formation, or combinations thereof.
 4. The method of claim1 wherein the semiconductor substrate is a silicon wafer.
 5. The methodof claim 1 wherein M is selected from the group of metals of Groups IIA,IVB, VA, VB, VIIIB, and IB.
 6. The method of claim 5 wherein M isselected from the group of Sr, Ba, Ti, Bi, Ta, Rh, Ir, Pd, Pt, Cu, andAg.
 7. The method of claim 6 wherein M is selected from the group of Sr,Ba, and Ti.
 8. The method of claim 1 wherein each R group isindependently H or a (C₁-C₄) alkyl moiety.
 9. The method of claim 1wherein each L is independently selected from the group of carbonyl,cyclopentadienyl, cyclooctadienyl, ethoxy, isopropoxy,vinyltrimethylsilane, and polyamine ligands.
 10. The method of claim 1wherein x=0, y=2, and M=Ba or Sr.
 11. The method of claim 1 wherein theprecursor composition is a liquid.
 12. The method of claim 1 wherein theprecursor composition is vaporized in the presence of a carrier gas. 13.The method of claim 1 wherein the precursor composition is vaporized inthe presence of a reaction gas.
 14. The method of claim 1 wherein themetal-containing film is a single metal or metal alloy film.
 15. Amethod of manufacturing a semiconductor structure, the methodcomprising: providing a semiconductor substrate or substrate assembly;providing a precursor composition comprising one or more organicsolvents and one or more complexes of the formula:

 wherein: M is a transition metal, main group metal, or lanthanide; eachY group is independently O or N—R³; L is a neutral or anionic supportingligand; each R group is independently H, or an organic group; x=0 to 6;n+ is the oxidation state of the metal; y=n if L is neutral, y=n−x if Lis monoanionic, or y=n−2x if L is dianionic; and vaporizing theprecursor composition to form vaporized precursor composition; anddirecting the vaporized precursor composition toward the semiconductorsubstrate or substrate assembly to form a metal-containing film on asurface of the semiconductor substrate or substrate assembly.
 16. Amethod of forming a film on a substrate, the method comprising:providing a substrate; providing a precursor composition comprising oneor more complexes of the formula:

 wherein: M is a transition metal, main group metal, or lanthanide; eachY group is independently O or N—R³; L is a neutral or anionic supportingligand; each R group is independently H, or an organic group; x=0 to 6;n+ is the oxidation state of the metal; y=n if L is neutral, y=n−x if Lis monoanionic, or y=n−2x if L is dianionic; and forming ametal-containing film from the precursor composition on a surface of thesubstrate.
 17. The method of claim 16 wherein the step of forming ametal-containing film comprises vaporizing the precursor composition anddirecting it toward the substrate using a chemical vapor depositiontechnique.
 18. The method of claim 17 wherein the precursor compositionis a liquid.
 19. A method of forming a film on a substrate, the methodcomprising: providing a substrate; providing a precursor compositioncomprising one or more solvents and one or more complexes of theformula:

 wherein: M is a transition metal, a main group metal, or a lanthanide;each Y group is independently O or N—R³; L is a neutral or anionicsupporting ligand; each R group is independently H, or an organic group;x=0 to 6; n+ is the oxidation state of the metal; y=n if L is neutral, y=n−x if L is monoanionic, or y=n−2x if L is dianionic; and vaporizingthe precursor composition to form vaporized precursor composition; anddirecting the vaporized precursor composition toward the substrate toform a metal-containing film on a surface of the substrate.